JP4357416B2 - Graft polyol and continuous process for producing the same - Google Patents

Abstract

Disclosed is a process for preparation of final graft polyols via a continuous process. In addition, a final graft polyol formed by the process is disclosed. The process includes the steps of reacting a plurality of ethylenically unsaturated monomers and a reaction moderator with a macromer having induced unsaturation in the presence of a carrier polyol, a free radical polymerization initiator, and a first graft polyol. The process provides for the preparation of a final graft polyol having a solids level of from 30 to 70 % in a continuous process. The final graft polyol produced by the process has a lower viscosity over a range of solids levels, a reduced amount of very large irregularly shaped particles, a reduced viscosity change in response to a change in reaction temperature compared to a typical graft polyol, a reduced tendency to foul the continuous reactor, and a braoder particle size distribution compared to an identical graft polyol prepared by a semi-batch process.

Description

  The present invention relates to a graft polyol, and further to a continuous process for producing a graft polyol. In this method, a small amount of the first graft polyol prepared in advance is used in the production of the graft polyol as the final product.

    Methods for producing graft polyols (also known as polymer polyols) are known in the art, and in the presence of carrier polyols, reaction modifiers, and radical polymerization initiators that copolymerize monomers and macromers. Usually, it involves the reaction of monomers with macromonomers. The disadvantages of current methods for producing graft polyols are that soils are prone to deposit in the reactor, which is a significant problem, especially in continuous reactors. When fouling occurs, the reactor quickly becomes clogged with sediment of unstable compounds in the reaction. For this reason, it is necessary to stop and clean the reactor, resulting in a loss in productivity in the reactor. Thus, it is considered to be very effective to obtain a continuous process for producing graft polyol which hardly causes contamination.

  This invention is made | formed in view of the said situation, The objective is to provide the continuous manufacturing method of the graft polyol which does not produce the stain | pollution | contamination by reaction easily.

  In order to achieve the above object, the present inventors include a) a first containing a vinyl polymer content of 3 to 20% by mass, a carrier polyol, a macromer having induced unsaturation, and one or more radical polymerization initiators. B) obtaining a second reaction stream comprising two or more ethylenically unsaturated monomers and a reaction modifier; c) in a continuous reactor, the first reaction stream; And continuously forming a final graft polyol having a solids level of 30 to 70% by weight.

  According to the present invention, there are provided a method for producing a graft polyol, and a graft polyol produced by continuous treatment according to this production method.

  According to a preferred embodiment of the present invention, an initial graft polyol with a vinyl polymer content of 3-20% by weight, a carrier polyol, a macromer with induced unsaturation, and one or more radical polymerization initiators A first reaction stream comprising: a second reaction stream comprising two or more ethylenically unsaturated monomers and a reaction modifier; and a first reaction stream and a second reaction stream in a continuous reactor. And a step of combining the two reaction streams to obtain a final graft polyol having a solid content of 30 to 70% by mass.

  According to a second embodiment of the present invention, it is a first graft polyol produced by a continuous process and having a solid content of 30 to 70% by mass, comprising two or more ethylenically unsaturated monomers and a reaction modifier. And a macromer having induced unsaturation, a carrier polyol, an initial graft polyol with a vinyl content of 3-20% by weight, and a final graft polyol in the presence of one or more radical polymerization initiators are provided. .

  According to another embodiment of the present invention, an initial graft polyol with a vinyl content of 3-20% by weight, a carrier polyol, a macromer with induced unsaturation, and one or more radical polymerization initiators, A method of continuously producing a final graft polyol having a solid content of 30 to 70% by mass is provided, including a step of reacting at least one type of ethylenically unsaturated monomer and a reaction modifier in a continuous reactor. The

  The above features and significant points of the present invention will be described in further detail below.

  According to the invention, in the presence of at least two ethylenically unsaturated monomers, a macromer with induced unsaturation, an initial graft polyol, at least one radical polymerization initiator, and a reaction modifier. A process for producing a final graft polyol with a solids level of 30-70% by weight, comprising the step of reacting with Each component used will be described in detail below.

  In a known process for the production of conventional polyether polyols, for example, alkylene oxides are added by base catalysis to initiator molecules or nuclei containing reactive hydrogen atoms, for example polyhydric alcohols. Examples of such polyhydric alcohols are glycerol, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, 1,2,6-hexanetriol, pentaerythritol, sucrose, and sorbitol. . Other suitable initiators include both aliphatic and aromatic compounds such as ethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,2-butenediol, 1,3-butenediol, 1,4- Examples include butenediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. Included within the term “polyhydric alcohol” are compounds derived from phenol, such as 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A). Examples of other suitable initiators of the polyether polyols of the present invention include hydrogenated starch hydrolysates, such as mannitol derivatives from Roquette, trade name Lycasin®. Polyether polyols are described in known methods, such as the method disclosed by Wurtz, 1859, Encyclopedia of Chemical Technology, Vol. 7, pages 257-262, Interscience Publishers, Inc. Publication (1951), or US Pat. No. 1,922,459. ing.

  Examples of useful alkylene oxides are ethylene oxide, propylene oxide, butylene oxide, amylene oxide, tetrahydrofuran, epihalohydrin, arylalkylene styrene, and mixtures thereof. Alkylene oxide may be added to the initiator molecule and chain extension is carried out by anionic or cationic polymerization in the presence of a catalyst.

  Examples of preferred alkoxylation catalysts are known substances such as potassium hydroxide, sodium hydroxide, potassium hydroxide alcoholate, sodium hydroxide alcoholate, cesium hydroxide, amine, Lewis acid catalyst or double metal complex catalyst.

  Graft polyols are usually defined as vinyl polymer dispersions in polyether polyols as outlined in US Reissue Patent Re. 33,291. Typical methods for producing graft polyols are known from the prior art. Prior art graft polyols are carrier polyols, reaction modifiers of polyether polyols with induced unsaturation, commonly known as macromers, and single ethylenically unsaturated monomers or mixtures of ethylenically unsaturated monomers. And in situ polymerization in the presence of a radical polymerization initiator.

  Generally, the induced unsaturation level of the macromer is 0.1 to 1.0 mole per molecule of polyol. As used herein and in the claims, the term macromer refers to a polyether polyol having induced unsaturation. Typical graft polyols, and the macromers used in making the initial and final graft polyols of the present invention, include all conventional polyols as described above, ethylenic unsaturations and carbonyls, anhydrides, isocyanates. It can be produced by reacting with an organic compound having both a nate, an epoxy group or other groups reactive to an active hydrogen-containing group. Examples of suitable unsaturated isocyanates are isocyanatoethyl methacrylate (IEM) and 1,1-dimethylmetaisopropenylbenzyl isocyanate (TMI). The macromer used to produce the final graft polyol of the present invention preferably has a number average molecular weight of 6000 Dalton or higher. Furthermore, the functionality of the macromer is preferably 3 or more.

  Representative examples of organic compounds having ethylenic unsaturation and reactive groups are maleic acid, maleic anhydride, fumaric acid, crotonic acid, crotonic anhydride, propenyl anhydride, acrylic acid, acryloyl chloride, hydroxyacrylate Ethyl, hydroxyethyl methacrylate, hydroxypropyl acrylate, or hydroxypropyl methacrylate, halogenated maleic acid and its anhydride, unsaturated polyhydric alcohols such as 2-butene-1,4-diol, glycerol allyl ether, trimethylol Propane allyl ether, pentaerythritol allyl ether, pentaerythritol vinyl ether, pentaerythritol diallyl ether, and 1-butene-3,4-diol, unsaturated epoxides such as 1-vinylcyclohexene-3,4-e Kishido, butadiene monoxide, vinyl glycidyl ether (1-vinyloxy-2,3-epoxy propane), a glycidyl methacrylate, 3-allyloxy-propylene oxide (allyl glycidyl ether). When a polycarboxylic acid or its anhydride is used to introduce an unsaturated bond into a polyol, it is used as a macromer of the present invention by reacting an unsaturated polyol with an alkylene oxide, preferably ethylene oxide or propylene oxide. It is preferable to remove the unreacted acid group before the treatment. The amount of alkylene oxide used is determined so as to reduce the acid value of the unsaturated polyol to less than 5.

  Representative ethylenically unsaturated monomers that can be used to make the first or final graft polyols of the present invention are butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, etc., substituted styrene, such as Cyanostyrene, nitrostyrene, N, N-dimethylaminostyrene, acetoxystyrene, methyl 4-vinylbenzoate, phenoxystyrene, p-vinylphenyl oxide, acrylic acid and substituted acrylic monomers such as acrylonitrile, acrylonitrile Acid, methacrylic acid, methyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, isopropyl methacrylate, octyl methacrylate, methacrylonitrile, α-ethoxyacryl Ethyl acetate, methyl α-acetaminoacrylate, butyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, N-butylacrylamide, Methacryloylformamide, etc., vinyl esters, vinyl ethers, vinyl ketones, etc., such as vinyl acetate, vinyl butyrate, isopropyl acetate, vinyl formate, vinyl acrylate, vinyl methacrylate, vinyl meth Ciacetate, vinyl benzoate, vinyl toluene, vinyl naphthalene, vinyl methyl ether, vinyl pyrrole ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro-1,2-pyran, 2-butoxy-2'-vinyloxydiethyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl phosphonate, such as vinyl phenyl ketone, vinyl ethyl sulfone, N-methyl-N -Vinylcetamide, N-vinylpyrrolidone, vinylimidazole, divinylsulfoxide, divinylsulfone, sodium vinylsulfonate, methyl vinylsulfonate, N-vinylpyrrole, etc. Dimethyl phosphate, dimethyl maleate, maleic acid, crotonic acid, fumaric acid, itaconic acid, monomethyl itaconate, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, glycidyl acrylate, allyl alcohol, glycol mono of itaconic acid Esters, vinyl pyridine and the like.

  Any known polymerizable ethylenically unsaturated monomer can be used, and the above-described compounds are merely examples of monomers preferably used in the present invention, and are not limited thereto. In a preferred embodiment of the invention, the monomer comprises acrylonitrile, styrene, and mixtures thereof. The mixture preferably contains 20-80% acrylonitrile and the remaining amount of styrene.

  The amount of the ethylenically unsaturated monomer used in the final graft polymerization reaction is usually 30 to 70% by mass with respect to the total mass of the product, and preferably 30 to 50% by mass of the monomer mass.

  Usable radical polymerization initiators are known radical polymerization initiators such as peroxides, persulfates, perborates, percarbonates, azo compounds and the like. Examples of these include hydrogen peroxide, dibenzoyl peroxide, acetyl peroxide, benzoyl hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, butyryl peroxide, diisopropyldibenzene hydroperoxide. Oxide, cumene hydroperoxide, paramentane hydroperoxide, diacetyl peroxide, di-α-cumyl peroxide, dipropyl peroxide, diisopropyl peroxide, isopropyl-t-butyl peroxide, butyl-t-butyl peroxide, Difuroyl peroxide, bis (triphenylmethyl) peroxide, bis (p-methoxybenzoyl) peroxide, p-monomethoxybenzoyl peroxide, rubene peroxide, ascaridol (essential oil peroxide), t- Tilperoxybenzoate, diethyl peroxyterephthalate, propyl hydroperoxide, isopropyl hydroperoxide, n-butyl hydroperoxide, t-butyl hydroperoxide, cyclohexyl hydroperoxide, transdecalin hydroperoxide, α-methylbenzyl Hydroperoxide, α-methyl-α-ethylbenzyl hydroperoxide, tetralin hydroperoxide, triphenylmethyl hydroperoxide, diphenylmethyl hydroperoxide, triphenylmethyl hydroperoxide, diphenylmethyl hydroperoxide, α, α '-Azobis- (2-methylheptonitrile), 1,1'-azobis (cyclohexanecarbonitrile), 4,4'-azobis- (4-cyanopentanoic acid), 2, '-Azobis (isobutyronitrile), 1-t-butylazo-1-cyanocyclohexane, peroxy acid, diisopropyl peroxycarbonate, 4,4'-azobis (2,4-dimethylvaleric acid nitrile), 2- t-butylazo-2-cyano-4-methoxy-4-methylpentane, 2,2′-azobis-2-methylbutanenitrile, 2-t-butylazo-2-cyanobutane, 1-t-amylazo-1-cyanocyclohexane 2,2′-azobis (2,4-dimethyl-4-methoxyvaleric acid nitrile), 2,2′-azobis-2-methylbutyronitrile, 2-t-butylazo-2-cyano-4-methylpentane 2-t-butylazo-2-isobutyronitrile, 2-butylperoxyisopropyl carbonate, 1,1-t-aminoperoxysic Mixtures of rhohexane, t-amylperoxy-2-ethylhexanoate, and the like, and an initiator can also be used. In a preferred embodiment of the invention, a mixture of 1,1-t-amylperoxycyclohexane and t-amylperoxy-2-ethylhexanoate is used as an initiator.

  In the graft polymerization reaction for producing the first graft polyol, generally, about 0.1% by mass to about 10.0% by mass of a radical polymerization initiator is used with respect to the total mass of monomers used. In the graft polymerization reaction to produce the final graft polyol, it is generally from about 0.1% to about 3.0% by weight, preferably from about 0.3% to about 1%, based on the total weight of monomers used. 0.0% by weight of radical polymerization initiator is used.

  In the present invention, it is necessary that a reaction modifier is present in the production of the final graft polyol, and it is optimal to use the reaction modifier in the production of the first graft polyol. The reaction modifier is preferably an alcohol, mercaptan, haloalkane, or a mixture thereof. The reaction adjustments that can be used are as follows. Acetic acid, bromoacetic acid, chloroacetic acid, ethyl dibromoacetate, iodoacetic acid, tribromoacetic acid, ethyl tribromoacetate, trichloroacetic acid, ethyl trichloroacetate, acetone, p-bromophenylacetonitrile, p-nitrophenylacetylene, allyl alcohol, 2, 4,6-trinitroaniline, p-ethynylanisole, 2,4,6-trinitroanisole, azobenzene, benzaldehyde, p-cyanobenzaldehyde, 2-butylbenzene, bromobenzene, 1,3,5-trinitrobenzene, benzochrysene , Ethyl trinitrobenzoate, benzoin, benzonitrile, benzopyrene, tributylborane, 1,4-butanediol, 3,4-epoxy-2-methyl-1-butene, 1-butyl ether, t-butyl isocyanate, 1-phenylbutyne, p-cresol, p-bromocumene, dibenzonaphthacene, p-dioxane, pentaphenylethane, ethanol, 1,1-diphenylethylene, ethylene glycol, ethyl ether, fluorene, N, N-dimethylformamide, 2 -Heptene, 2-hexene, isobutyral aldehyde, heptene, 2-hexene, isobutyral aldehyde, diethyl bromomalonate, bromotrichloromethane, dibromoethane, diiodomethane, naphthalene, 1-naphthol, 2-naphthol, methyl oleate, 2, 4,4-triphenyl-1-pentene, 4-methyl-2-pentene, 2,6-diisopropylphenol, phenyl ether, phenylphosphine, diethylphosphine, dibutylphosphine, phosphorus trichloride, , 1,1-tribromopropane, dialkylphthalate, 1,2-propanediol, 3-phosphinepropionitrile, 1-propanol, pyrocatechol, pyrogallol, 1,4-benzoquinone, methyl stearate, tetraethylsilane, triethyl Silane, bromostilbene, α-bromostyrene, α-methylstyrene, tetraphenylsuccinonitrile, 2,4,6-trinitrotoluene, p-toluidine, N, N-dimethyl-p-toluidine, α-cyano-p- Tolunitrile, α, α'-dibromo-p-xylene, 2,6-xylenol, diethylzinc, dithiodiacetic acid, ethyldithioniacetic acid, 4'4-dithio-bisanthranilic acid, benzeneethiol, o-ethoxybenzenethiol, 2 , 2'-dithiodiacetic acid, 4,4'-dithio Bisanthranilic acid, benzenethiol, o-ethylbenzenethiol, 2,2'-dithiobisbenzothiazole, benzyl sulfide, 1-dodecanethiol, ethanethiol, 1-hexanethiol, 1-naphthalenethiol, 2-naphthalenethiol, 1- Octanethiol, 1-heptanethiol, 2-octanethiol, 1-tetradecanethiol, benzylthiol, isopropanol, 2-butanol, carbon tetrabromide, bromotrichloromethane, t-dodecyl mercaptan, and various combinations of these compounds Can be mentioned. Preferred reaction modifiers are 2-propanol, 2-butanol and mixtures thereof. The amount of reaction modifier used is preferably in the range of 0.5 to 25% by mass relative to the total mass of monomers.

  The carrier polyol used to form either the initial graft polyol or the final graft polyol of the present invention may comprise any of the conventional polyols described above and is a hydrogenated starch hydrolyzate as an initiator. What was obtained using is also included. The carrier polyol used to form the initial graft polyol and the final graft polyol of the present invention need not be the same, but may be the same. The carrier polyol may contain 0 to 30% by mass of propylene oxide having an ethylene oxide cap in addition to the initiator. In addition, the carrier polyol may contain a mixture of an initiator and a different (a plurality of) alkylene oxides with or without an ethylene oxide or propylene oxide cap. The desired carrier polyol properties are determined in part by the desired properties of the foam produced using the final graft polyol.

  In the operation of the present invention, the first step is to produce the first graft polyol. The initial graft polyol is usually obtained by reacting one monomer or monomer mixture with a macromer having an induced unsaturated bond in the presence of a carrier polyol, a radical polymerization initiator and optionally a reaction modifier. It is manufactured by the method. The reaction is carried out in a batch reactor by a batch or semi-batch process and produces the first graft polyol with a reasonably narrow and uniform particle size distribution, generally having a vinyl polymer content of 3-20% by weight. The vinyl polymer content of the first graft polyol is preferably 3 to 15% by mass, and more preferably 5 to 10% by mass. Vinyl polymer content is calculated by dividing the total mass of ethylenically unsaturated monomers used in the initial graft polyol formation reaction by the total product mass, ie the total mass of the initial graft polyol, and multiplying this result by 100. Is calculated by The carrier polyol, macromer, reaction modifier, and radical polymerization initiator are as described above. The polymerization reaction is usually performed in a temperature range of 25 ° C to 180 ° C, more preferably 90 ° C to 135 ° C. The monomer used is preferably a mixture of styrene and acrylonitrile in which 20-80% by mass of acrylonitrile is used and the remainder is styrene. Usually, the reactor is first charged with a portion of the macromer and carrier polyol. Macromers are generally in the range of 50-500% by weight, based on the total weight of monomers used. The proportion of the macromer used is more preferably 100 to 300% by mass and most preferably 150 to 250% by mass based on the total mass of monomers used in the reaction. The reactor was then heated to the reaction temperature, the first stream containing additional carrier polyol and radical polymerization initiator was combined with the second stream containing monomer, and the resulting combined stream was fed to the reactor. Usually, the product can be separated (strip) under reduced pressure and stabilized by adding di-t-butyl-p-cresol (BHT).

  In the second step of operation, the final graft polyol is formed using a continuous reactor. The final graft polyol preferably has a solid level of 30 to 70% by mass, more preferably 30 to 50% by mass, and most preferably 40 to 50% by mass. First, the reactor is charged with the final graft polyol or macromer produced as described above and a portion of the carrier polyol. A first reaction stream is then formed comprising the first graft polyol described above, a carrier polyol, a macromer having induced unsaturated bonds, and at least one radical polymerization initiator and is continuously fed to the reactor. The initial graft polyol is preferably present in an amount of 1 to 20% by weight, more preferably 3 to 15% by weight, and most preferably 5 to 10% by weight, based on the total weight of the monomers. The macromer is preferably present in an amount of 2 to 10% by weight, more preferably 2 to 8% by weight, based on the total weight of the monomers. The macromer should have an induced unsaturation of 0.1 to 1.0 mole, more preferably 0.2 to 0.8 mole per mole of macromer. A second reaction stream comprising monomer and reaction modifier is formed and continuously fed to the reactor. The continuous reactor is usually operated at a temperature of 25 ° C to 180 ° C, preferably 90 ° C to 150 ° C. The final graft polyol product is continuously recovered. The recovered product is generally separated under reduced pressure, but may be stabilized by adding a known stabilizer. Specific examples and comparative examples of this operation are shown below. As can be understood by those skilled in the art, this operation can be modified in various ways. In one embodiment, the two reaction streams may be mixed prior to introduction into the continuous reactor. Furthermore, each reaction stream may contain any mixture of reaction components, for example, the first reaction stream may contain other than monomers or reaction modifiers and other components. Similarly, the second reaction stream may contain an initial graft polyol, macromer, carrier polyol, radical polymerization initiator, or any mixture thereof.

Macromer A
Macromer A is produced by maleic anhydride and glycerin initiation as described above and includes 20% by weight ethylene oxide based on the total weight of the polyol and 5% by weight ethylene oxide cap based on the total weight of the polyol. Produced by reaction with a polyol produced with a glycerin initiator containing moiety. The remainder of the macromer contains a glycerin initiator and propylene oxide. Macromers have about 0.4 moles of induced unsaturation. The polyol used to make the macromer has a theoretical number average molecular weight of about 5500 daltons and a hydroxyl number of 25. The initial reaction product is isomerized to form a fumarate derivative and capped with propylene oxide. This technique is well known and is disclosed in US Reissue Pat. No. 33291, which is a reissue of US Pat. No. 4,454,255, incorporated herein by reference.

Macromer B
Macromer B is a TMI modified polyol based on glycerol initiation. The glycerin-initiated polyol has an ethylene oxide cap of 21% by mass with respect to the total mass, and the remaining amount contains glycerin initiator and propylene oxide. The theoretical number average molecular weight of the polyol is about 6,120, and its hydroxyl number is 27.5. About 0.3 mole of TMI is added per mole of macromer. The reaction is carried out in the presence of dibutyltin dilaurate. The reaction is stopped by the addition of benzoyl chloride.

Polyol A
Polyol A is a glycerol-initiated polyol having an ethylene oxide cap of about 18.5% by weight relative to the total weight and having a hydroxyl number of 35.

Polyol B
Polyol B is a trimethylolpropane-initiated polyol having an ethylene oxide cap of about 13% by weight relative to the total weight and a hydroxyl number of 35.

Production of the first graft polyol according to the invention As mentioned above, the first graft polyol according to the invention is produced with a vinyl polymer content of 3-20% by weight measured by the amount of monomer used in the reaction. Is common. By changing the amount of monomer used, the vinyl polymer content of the first known graft polyol changes. An example for producing a graft polyol having a vinyl polymer content of about 8% by weight is described below. The reaction is carried out in a batch reactor with a coating of 1 liter capacity under a nitrogen atmosphere. The reaction temperature is 125 ° C. and a stirring speed of about 300 rpm is used. The reactor is initially charged with 96.0 g of Macromer B and 356 g of polyol. The reactor is fed with a first stream comprising 24 g acrylonitrile and 24 g styrene. The reactor is then fed with a second stream comprising 100 g of polyol A and 3 g of t-amylperoxy-2-ethylhexanoate. The monomer stream was fed over 50 minutes and the feed stream containing polyol A was fed in about 60 minutes. These feed streams are added by a static mixer. The reaction time is about 30 minutes. After 30 minutes of reaction of the mixture, it was stripped for 30 minutes at about 1 mm Hg under reduced pressure. The initial graft polyol obtained is stabilized with 0.05 wt% PHT.

Production of comparative graft polyol for comparison by a continuous process not according to the invention A final graft polyol for comparison was produced using a continuous reactor. The solid fraction of the final graft polyol is determined by the monomer used in the reaction. In this way, products with different solid content (levels) can be obtained by changing the amount used. Specific examples of the final graft polyol according to the comparative example are shown below.

  A continuous reactor is first charged with 300 g of the desired final graft polyol. The reaction temperature is 135 ° C., and the stirring speed is about 1500 rpm. The capacity of the continuous reactor is about 300 ml. The first reaction stream contains 3034 g of polyol B, 127 g of macromer A, 9 g of 1,1-t-aminoperoxycyclohexane, and 5 g of t-amylperoxy-2-ethylhexanoate. The second reaction stream contains 940 g acrylonitrile, 1880 g styrene, and 423 g 2-butanol. The second reaction stream is fed to the continuous reactor by a static mixer and the product is continuously produced and recovered. The first 180 minutes of product was collected and discarded, and the last 20 minutes of product was collected and vacuum stripped at 125 ° C. and about 1 mmHg for 30 hours. The viscosity of the final polyol for comparison was about 12800 mPa.s at 25 ° C.

Production of the final graft polyol by the continuous process of the present invention The final graft polyol of the present invention is prepared by reducing the amount of polyol B in the first stream to 2835 g and adding 199 g of the first graft polyol produced as described above to the first reaction stream. Except for the above, the final graft polyol of the present invention was produced by the above-described method for producing the final graft polyol for comparison. This gives a final graft polyol in an amount of the first graft polyol of about 7% by weight, based on the weight of the monomer. The reaction conditions are the same as those described for the final graft polyol for comparison. As described for the comparative final graft polyol, the final solids content can be varied and is known to those skilled in the art.

  Using the process of the present invention to produce the final graft polyol reduces the fouling of the continuous reactor system by half. This means that the reaction can be carried out at least twice as long before a shutdown for cleaning the continuous reactor system is required.

Production of comparative final graft polyol by semi-batch method not according to the production method of the present invention The reaction was carried out in a 500 ml stainless steel pressurized semi-batch reactor under nitrogen atmosphere. The reaction temperature is 135 ° C. and a stirring speed of about 300 rpm is used. The reactor is initially charged with 9.5 g of Macromer A, 15.0 g of the first polyol prepared as described above, 32.0 g of 2-butanol, and 96.0 g of polyol B, and the reaction temperature. Heat to. The reactor is then fed with a first stream containing 70 g acrylonitrile and 140.0 g styrene. In addition, a second stream containing 120.0 g of polyol B, 0.4 g of t-aminoperoxy-2-ethylhexanoate, and 0.7 g of 1,1-t-amylperoxycyclohexane is added to the reactor. To feed. The monomer stream was fed over 180 minutes and the feed stream containing polyol B was fed in about 190 minutes. These feed streams are added by a static mixer. After the addition of this two feed stream, the reaction continues for 30 minutes. After a further 30 minutes of reaction, stripping was performed at 125 ° C. and about 1 mmHg for 30 minutes under reduced pressure. A comparative final graft polyol was prepared in substantially the same manner as the final graft polyol of the present invention, maintaining the proportion of reactants substantially the same, with only changes in the form of the reaction. The product has a viscosity at 25 ° C. of about 20,700 mPa.s, which is significantly higher than the viscosity of the final graft polyol produced according to the present invention described in the drawings described below.

  FIG. 1 is a scanning electron micrograph of a comparative graft polyol produced by the above method. The particles are formed very unevenly, and very large non-uniformly shaped particles are formed in addition to small particles. On the other hand, FIG. 2 is a scanning electron micrograph of the final graft polyol manufactured according to the present invention manufactured as described above. The particles are very uniform, have a spherical outer diameter, and the particle size distribution is narrower than for comparative graft polyols produced by a continuous process. The final graft polyol of the present invention does not contain very large non-uniformly shaped particles as shown in FIG. The very large particles shown in FIG. 1 are believed to be responsible for the fouling of the continuous reactor, which requires a shutdown to clean the continuous reactor.

  In FIG. 3, the effect of the reaction temperature on the viscosity of the comparative final graft polyol is indicated by reference numeral 10. The comparative final graft polyol is very sensitive to the reaction temperature, and even when the reaction temperature changes from 131 ° C. to 134 ° C. by only 3 ° C., the viscosity changes in the range of 30000 mPa · s to 14000 mPa · s. Unlike this, the viscosity of the final graft polyol produced according to the present invention is indicated by reference numeral 20 in FIG. 3 and is constant without being affected even when the reaction temperature changes in the range of 131 ° C. to 137 ° C. The viscosity is considerably lower than that of the comparative example, which is about 12000 mPa.s.

  FIG. 4 shows the effect of the solids content on the viscosity of the final product for the comparative final graft polyol (symbol 30) and the final graft polyol produced according to the invention (symbol 40). The final graft polyols produced according to the invention always have a very low viscosity, a low viscosity with a difference of about 3000 mPa.s.

  FIG. 5 shows the particle size distribution of a comparative final graft polyol produced by the method described above (reference number 50). The particle size distribution of the above-mentioned final graft polyol produced according to the present invention is indicated by reference numeral 60. The shapes of these two curves are similar. However, although the peak value is approximately 1.05 microns, the final graft polyol (60) of the present invention shows a somewhat narrow particle size distribution. In FIG. 6, the particle size distribution of the comparative final graft polyol produced by the semi-batch method is indicated by reference numeral 70. For comparison, the particle size distribution of the final graft polyol of the present invention is indicated by reference numeral 80 in FIG. The particle size distribution in this case is much larger than in the final graft polyol of the present invention. The comparative final graft polyol (70) produced by the semi-batch method has a lower main peak at 0.25 microns and a second peak at about 1.05 microns. The comparative final graft polyol (70) is substantially free of granules larger than about 2.45 microns. In contrast, the final graft polyol (80) of the present invention has a small peak below about 0.25 microns, a main peak at about 1.05 microns, and particles larger than about 2.45 microns. Is included in a considerable number.

  Since the above invention is described in accordance with relevant legal standards, it is described by way of example rather than the original limitation. It will be apparent to those skilled in the art that modifications and variations can be made to the above-described embodiments, and can be made without departing from the scope of the present invention. The protection scope of the present invention is set forth in the following claims.

It is a scanning electron micrograph of the comparative graft polyol which is not based on the manufacturing method of this invention. It is a scanning electron micrograph of the graft polyol manufactured by the method of this invention. It is a graph for comparing the influence of the reaction temperature of the comparative graft polyol, which is not based on the production method of the present invention, on the viscosity with the effect of the final graft polyol produced by the method of the present invention on the viscosity of the reaction temperature. . To compare the effect of the solid content of the comparative graft polyol not on the viscosity with the method of the present invention on the viscosity of the solid content of the final graft polyol produced by the method of the present invention on the viscosity It is a graph. FIG. 3 is a graph for comparing the particle size distribution of a final graft polyol produced by the continuous production method of the present invention and the particle size distribution of a graft polyol produced by a continuous method not using the method of the present invention. is there. FIG. 4 is a graph for comparing the particle size distribution of a final graft polyol produced by the continuous production method of the present invention and the particle size distribution of a graft polyol produced by a semi-batch method not using the method of the present invention. .

Claims (51)

a ′) reacting two or more ethylenically unsaturated monomers, a polyether polyol as a carrier polyol, one or more radical polymerization initiators, and a polyether polyol having induced unsaturation as a macromer to produce ethylene Obtaining an initial graft polyol having a polymer content of 3 to 20% by weight of the unsaturated unsaturated monomer,
a) obtaining a first reaction stream comprising said first graft polyol , polyether polyol as carrier polyol, polyether polyol having induced unsaturation as macromer , and one or more radical polymerization initiators;
b) obtaining a second reaction stream comprising two or more ethylenically unsaturated monomers and a reaction modifier;
c) combining the first reaction stream and the second reaction stream in a continuous reactor to continuously form a final graft polyol having a solids content of 30-70% by weight. Continuous manufacturing method. The production method according to claim 1, wherein step a) comprises producing 1 to 20% by weight of the first graft polyol based on the total mass of the two or more ethylenically unsaturated monomers of step b) .   The production method according to claim 1, wherein the first reaction stream contains a mixture of two or more kinds of radical polymerization initiators.   The production method according to claim 3, wherein a mixture of 1,1-t-amylperoxycyclohexane and t-amylperoxy-2-ethylhexanoate is used as the two or more kinds of radical polymerization initiators. The manufacturing method of Claim 1 whose solid content of a final graft polyol is 30-50 mass%.   The step a) uses at least one macromer of a fumarate-modified polyol, a maleic acid-modified polyol, a maleic anhydride-modified polyol, or a 1,1-dimethylmetaisopropenyl benzyl isocyanate-modified polyol. Manufacturing method.   The process according to claim 1, wherein a macromer having an induced unsaturation level of 0.1 to 1.0 mole per mole is used. Macromer formation by reacting a polyol polymerized using a hydrogenated starch hydrolyzate as an initiator with an organic compound containing both ethylenically unsaturated and active hydrogen-containing groups reactive groups The manufacturing method according to claim 1, further comprising:   The production method according to claim 1, wherein a macromer having a number average molecular weight of 6000 daltons or more is used.   The production method according to claim 1, wherein a macromer having a functionality of 3 or more is used.   The manufacturing method of Claim 1 using 2-10 mass% macromer with respect to monomer total mass.   The process according to claim 1, wherein in step b), a mixture of acrylonitrile and styrene is used as the two or more types of ethylenically unsaturated monomers.   The process according to claim 12, wherein in step b) acrylonitrile comprises a mixture of 20 to 80% by weight of ethylenically unsaturated monomers and styrene comprises the remaining amount of said monomers.   The process according to claim 1, wherein in step b) 0.5 to 25% by weight of reaction modifier is used with respect to the total weight of monomers.   The process according to claim 1, wherein 2-butanol, isopropanol, or a mixture thereof is used as a reaction modifier in step b). The process according to claim 1 , wherein the first graft polyol is obtained in a batch reactor. Fumarate-modified polyols, maleic acid-modified polyol, with either one or more macromers of maleic anhydride-modified polyols, or 1,1-dimethyl meta-isopropenyl benzyl isocyanate modified polyol, to obtain a first graft polyol, wherein Item 2. The manufacturing method according to Item 1 . With Ma Cromer, get the first graft polyol used in the range of 50 to 500% by weight of the macromer relative to the total weight of the monomers used to obtain the first graft polyol, a manufacturing method of claim 1. Solid content 30-70 produced by a continuous process and containing reaction products in the presence of two or more ethylenically unsaturated monomers, a reaction modifier, and an initial graft polyol, and one or more radical polymerization initiators % By weight of the final graft polyol,
The first graft polyol reacts with two or more ethylenically unsaturated monomers, a polyether polyol as a carrier polyol, one or more radical polymerization initiators, and a polyether polyol with induced unsaturation as a macromer. A final graft polyol characterized by being a graft polyol having a polymer content of 3 to 20% by mass of an ethylenically unsaturated monomer . 20. The final graft polyol of claim 19 , wherein the two or more ethylenically unsaturated monomers comprise a mixture of acrylonitrile and styrene. 21. The final graft polyol according to claim 20 , wherein the mixture of acrylonitrile and styrene contains 20-80% by weight acrylonitrile and the balance of styrene. 20. The final graft polyol according to claim 19 , wherein the initial graft polyol is present in an amount of 1 to 20% by weight, based on the total weight of monomers. The macromer used to produce the final graft polyol is at least one of a fumarate-modified polyol, a maleic acid-modified polyol, a maleic anhydride-modified polyol, or a 1,1-dimethylmeta-isopropenyl benzyl isocyanate-modified polyol. 20. The final graft polyol of claim 19 . 20. The final graft polyol of claim 19 , wherein the induced level of unsaturation of the macromer is 0.1 to 1.0 mole per mole of macromer. A reaction product of a polyol polymerized using a starch hydrolyzate with hydrogenated macromer as an initiator and an organic compound containing both ethylenically unsaturated and active hydrogen-containing groups reactive groups, 20. The final graft polyol of claim 19 . The final graft polyol according to claim 19 , wherein a macromer having a number average molecular weight of 6000 daltons or more is used. 20. The final graft polyol of claim 19 , wherein the functionality of the macromer is 3 or higher. 20. The final graft polyol according to claim 19 , wherein the macromer is present in an amount of 2 to 10% by weight relative to the total weight of monomers. 20. The final graft polyol according to claim 19 , wherein the reaction modifier is present in an amount of 0.5 to 25% by weight relative to the total weight of monomers. 20. The final graft polyol of claim 19 , wherein the reaction modifier comprises 2-butanol, isopropanol, or a mixture thereof. 20. The final graft polyol of claim 19 , wherein the one or more radical polymerization initiators include 1,1-t-aminoperoxycyclohexane, t-aminoperoxy-2-ethylhexanoate, or a mixture thereof. . 20. The final graft polyol of claim 19 , wherein the initial graft polyol is produced in a batch reactor. The macromer used to produce the first graft polyol is one or more of fumarate modified polyol, maleic acid modified polyol, maleic anhydride modified polyol, or 1,1-dimethylmetaisopropenyl benzyl isocyanate modified polyol The final graft polyol of claim 19 , wherein Ethylene, obtained by reacting two or more types of ethylenically unsaturated monomers, a polyether polyol as a carrier polyol, one or more radical polymerization initiators, and a polyether polyol having induced unsaturation as a macromer An initial graft polyol with a polymer content of unsaturated monomers of 3 to 20% by weight , a polyether polyol as carrier polyol, a polyether polyol with induced unsaturation as macromer and one or more radical polymerization initiators, A series of final graft polyols, which are reacted with another two or more ethylenically unsaturated monomers and a reaction modifier in a continuous reactor to continuously produce a final graft polyol having a solid content of 30 to 70% by mass. Manufacturing method. The production method according to claim 34 , wherein 1 to 20% by mass of the first graft polyol is used relative to the total mass of two or more other ethylenically unsaturated monomers. The production method according to claim 34 , wherein a mixture of two or more types of radical polymerization initiators is used. The production method according to claim 34 , wherein a mixture of 1,1-t-amylperoxycyclohexane and t-amylperoxy-2-ethylhexanoate is used as two or more kinds of radical polymerization initiators. The manufacturing method of Claim 34 whose solid content of a final graft polyol is 30-50 mass%. The process according to claim 34 , wherein a macromer having an induced unsaturation level of 0.1 to 1.0 mole per mole is used. A macromer is produced by reacting a polyol polymerized using a hydrogenated starch hydrolyzate as an initiator with an organic compound containing both ethylenic unsaturation and groups reactive to active hydrogen-containing groups. The manufacturing method according to claim 34 , further comprising the step of: The production method according to claim 34 , wherein a macromer having a number average molecular weight of 6000 daltons or more is used. The production method according to claim 34 , wherein the functionality of the macromer is 3 or more. The manufacturing method of Claim 34 using a 2-10 mass% macromer with respect to the total mass of a monomer. The production method according to claim 34 , wherein a mixture of acrylonitrile and styrene is used as two or more kinds of ethylenically unsaturated monomers. The process according to claim 34 , wherein the acrylonitrile comprises a mixture of 20-80% by weight of ethylenically unsaturated monomers and the styrene comprises the remaining amount of monomers. The production method according to claim 34 , wherein 0.5 to 25% by mass of a reaction modifier is used with respect to the total mass of the monomers. The production method according to claim 34 , comprising 2-butanol, isopropanol, or a mixture thereof as a reaction modifier. The production method according to claim 34 , wherein the macromer is at least one of fumarate-modified polyol, maleic acid-modified polyol, maleic anhydride-modified polyol, and 1,1-dimethylmetaisopropenyl benzyl isocyanate-modified polyol. 35. A process according to claim 34 comprising the other step of producing the initial graft polyol in a batch reactor. Fumarate-modified polyols, maleic acid-modified polyol, to produce a first graft polyol with maleic acid-modified polyols anhydride, one or more macromers of 1,1-dimethyl-meta-isopropenyl benzyl isocyanate modified polyol, according to claim 34 Manufacturing method. With Ma Cromer, to produce a first graft polyol with a macromer relative to the total weight of the monomers used to obtain the first graft polyol in the range of 50 to 500 wt%, manufactured according to claim 34 Method.

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